Chemical product production method, chemical product production apparatus, and fluid material

Abstract

A chemical product production method according to the present disclosure involves: introducing an inert gas into a reactor accommodating a fluid material containing a calcium compound to cause the fluid material to flow; heating the reactor; and supplying a starting material that contains a plastic to the heated reactor. The chemical product contains ethylene and propylene.

Description

Method for manufacturing chemicals, apparatus for manufacturing chemicals, and fluid materials.

[0001] This disclosure relates to a method for producing chemicals, an apparatus for producing chemicals, and a fluid material.

[0002] One method of recycling waste plastics is chemical recycling, which involves decomposing waste plastics, monomerizing and gasifying them, or using them as blast furnace reducing agents or coke oven raw materials. For example, a fluidized bed reactor is generally used in continuous reactors that use mixed plastics containing polyolefins as raw materials to obtain basic chemicals in a single stage without going through intermediate products such as pyrolysis oils.

[0003] Patent Document 1 discloses that a plastic powder, which is a mixture of polyolefins, polystyrene, polyethylene terephthalate (PET), etc., is supplied to a fluidized bed reactor and decomposed to obtain C2 to C4 olefins, that the heating medium in the fluidized bed is a mixture of used fluid catalytic cracking (FCC) catalyst and ZSM-5, and that these catalysts may also contain binder materials such as alumina or silica.

[0004] Special table 2016-513147 publication

[0005] This disclosure aims to provide a method for producing chemicals that can efficiently obtain ethylene and propylene in high yield.

[0006] The means for solving the above problems are as follows: <1> A method for producing a chemical product, comprising: introducing an inert gas into a reactor containing a fluid material containing a calcium compound and causing the fluid material to flow; heating the reactor; and supplying a raw material containing plastic to the heated reactor, wherein the chemical product contains ethylene and propylene. <2> The method for producing a chemical product according to <1>, wherein the calcium compound contains calcium oxide. <3> The method for producing a chemical product according to <1> or <2>, wherein the particle size of the fluid material is 0.3 mm or less. <4> The method for producing a chemical product according to any one of <1> to <3>, wherein the heating temperature of the reactor is 650°C or more and 1,000°C or less. <5> The method for producing a chemical product according to any one of <1> to <4>, wherein the raw material containing plastic contains a mixed plastic containing polyethylene and polypropylene. <6> A chemical manufacturing apparatus comprising: a reactor containing a fluid material containing a calcium compound; a raw material supply unit connected to the reactor and supplying raw materials containing plastic to the reactor; an inert gas supply unit connected to one end of the reactor and arranged to supply inert gas to the fluid material from the opposite direction to gravity; and a heating unit for heating the fluid material. <7> The chemical manufacturing apparatus according to <6>, wherein the calcium compound contains calcium oxide. <8> A fluid material used in a fluidized bed for the thermal decomposition of raw materials containing plastic, characterized in that it contains a calcium compound. <9> The fluid material according to <8>, wherein the calcium compound contains calcium oxide. <10> A method of using a fluid material, characterized in that the fluid material containing a calcium compound is used in a fluidized bed for the thermal decomposition of raw materials containing plastic. <11> A method of using a fluid material used to manufacture chemicals by thermal decomposing raw materials containing plastic, characterized in that the fluid material contains a fluid calcium compound.

[0007] According to embodiments of this disclosure, it is possible to provide a method for producing chemicals that can efficiently obtain ethylene and propylene in high yield.

[0008] Figure 1 is a schematic cross-sectional view showing an example of a chemical manufacturing apparatus according to the present disclosure.

[0009] The embodiments of this disclosure will be described in detail below. However, the embodiments are not limited to the following description and may be modified as appropriate without departing from the gist of this disclosure. Furthermore, in this specification, the "~" indicating a numerical range means that the numbers described before and after it are included as the lower and upper limits, respectively, unless otherwise specified. In numerical ranges described in stages within this disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages.

[0010] (Method for manufacturing a chemical product) The method for manufacturing a chemical product according to the present disclosure comprises introducing an inert gas into a reactor containing a fluid material containing a calcium compound, causing the fluid material to flow, heating the reactor, and supplying a raw material containing a plastic to the heated reactor, wherein the chemical product contains ethylene and propylene. The method for manufacturing a chemical product according to the present disclosure may further include other processes as necessary.

[0011] The method disclosed in Patent Document 1 primarily uses a mixture of FCC (Fluid Catalytic Cracking) catalyst and ZSM-5 for the decomposition of plastics, and does not optimize the conditions of the fluidized bed reaction in the thermal decomposition of plastics.

[0012] In response to this, the inventors conducted diligent research and discovered that ethylene and propylene can be efficiently obtained in high yield by heating raw materials containing plastic while a fluid material containing a calcium compound is flowing.

[0013] -Chemicals- The chemicals produced by the chemical manufacturing method of this disclosure are not particularly limited as long as they are chemicals obtained by decomposing raw materials including plastics, and can be appropriately selected according to the purpose. However, they are preferably chemicals containing ethylene and propylene, and more preferably chemicals containing an olefin having 4 carbon atoms in addition to ethylene and propylene.

[0014] Furthermore, the chemicals produced by the chemical manufacturing method of this disclosure may contain aromatic hydrocarbons.

[0015] Therefore, in this disclosure, “useful component” means at least one chemical selected from the group consisting of olefins having 2 to 4 carbon atoms and aromatic hydrocarbons.

[0016] --Olefins having 2 to 4 carbon atoms-- In this disclosure, olefins having 2 to 4 carbon atoms may be referred to as "lower olefins". The olefin having 2 to 4 carbon atoms is preferably at least one selected from the group consisting of alkenes having 2 to 4 carbon atoms and dienes having 2 to 4 carbon atoms, and alkenes having 2 to 4 carbon atoms are more preferred.

[0017] Examples of olefins having four carbon atoms include trans-2-butene, 1-butene, 2-methylpropene, cis-2-butene, 1,3-butadiene, and isobutene.

[0018] Among these, the method for producing the chemicals described herein has the advantage of high yields of ethylene and propylene. There are no particular restrictions on the yield (mass%) of ethylene and propylene, and they can be appropriately selected depending on the purpose, but it is preferably 30% by mass or more, more preferably 32% by mass or more, and even more preferably 33% by mass or more, relative to the mass of the raw materials including plastic. The total yield (mass%) of ethylene and propylene is preferably as high as possible, and there are no particular restrictions on its upper limit, for example, it may be 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0019] In this disclosure, the "yield" for each component and the "total yield" refer to the mass percentage (mass%) of each component relative to the raw material containing the plastic.

[0020] There are no particular restrictions on the total yield (mass%) of olefins having 2 to 4 carbon atoms, and it can be appropriately selected depending on the purpose. However, it is preferably 45% to 90% by mass, more preferably 50% to 70% by mass, and even more preferably 55% to 65% by mass, relative to the mass of the raw materials including the plastic.

[0021] Olefins with 2 to 4 carbon atoms can be used as basic chemicals suitable for chemical recycling and can serve as raw materials for polyolefins. Polyolefins can be suitably used in a variety of fields, such as shopping bags, plastic wrap, straws, medical devices, home appliance casings, erasers, hoses, tires, tubes, CD cases, food trays, food containers, plastic bottles, and fibers.

[0022] --Aromatic hydrocarbons-- There are no particular restrictions on aromatic hydrocarbons, but benzene, toluene, ethylbenzene, and the three positional isomers of xylene (p-xylene, m-xylene, and o-xylene), and styrene are preferred, and the three positional isomers of benzene, toluene, and xylene are more preferred.

[0023] In this disclosure, benzene, toluene, ethylbenzene, and the three positional isomers of xylene (p-xylene, m-xylene, and o-xylene), as well as styrene, may be referred to as "useful aromatic hydrocarbons."

[0024] There are no particular restrictions on the total yield (mass%) of useful aromatic hydrocarbons in chemical products, and it can be appropriately selected depending on the purpose. However, it is preferably 3% to 50% by mass, more preferably 4% to 40% by mass, and even more preferably 5% to 30% by mass, relative to the mass of the raw materials including plastics.

[0025] -By-products- Chemicals obtained by the chemical manufacturing methods of this disclosure may contain by-products. Examples of by-products include paraffin, carbon, and hydrogen gas. Carbon as a by-product refers to a composition consisting only of carbon atoms, and examples include soot, graphite, and diamond.

[0026] There are no particular restrictions on the paraffin, but examples include aliphatic saturated hydrocarbons having 1 to 4 carbon atoms, with aliphatic saturated hydrocarbons having 2 to 4 carbon atoms being preferred. Examples of aliphatic saturated hydrocarbons having 1 to 4 carbon atoms include chain-like aliphatic saturated hydrocarbons having 1 to 4 carbon atoms.

[0027] Specific examples of paraffins include methane, ethane, propane, isobutane, and n-butane. Among these, the method for producing the chemicals described herein has a low selectivity for methane.

[0028] There are no particular restrictions on the total yield (mass%) of paraffins having 1 to 4 carbon atoms, but it is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less, relative to the mass of the raw materials including plastic. The lower limit of the total yield (mass%) of paraffins having 1 to 4 carbon atoms is preferable as it is lower, for example, 0.1% by mass or more, relative to the mass of the raw materials including plastic.

[0029] The content of useful components and by-products in a chemical product can be determined by analyzing the gaseous and liquid products obtained as products of the chemical product manufacturing method of this disclosure using a gas chromatograph (GC) equipped with a flame ionization detector.

[0030] When analyzing the gaseous products as byproducts, the analysis can be performed using gas chromatography (GC) equipped with a flame ionization detector under the analytical conditions described in the examples. Each component can then be quantified using the internal standard method, based on the ratio of the peak area of ​​each component to that of the internal standard. The internal standard is not particularly limited as long as it is stable under the analytical conditions and easily separated from the analyte; for example, cyclopentane can be used.

[0031] Furthermore, when analyzing the liquid substance as a product, it can be analyzed using gas chromatography (GC) equipped with a flame ionization detector under the analytical conditions described in the examples, and each component can be quantified by the internal standard method based on the ratio of the peak area of ​​each component to that of the internal standard. The internal standard is not particularly limited as long as it is stable under the analytical conditions and easily separated from the analyte; for example, cyclopentane can be used.

[0032] Furthermore, the content of by-products such as coking residues in chemical products can be calculated by burning the fluid material with air inside the reactor and measuring the weight change before and after air calcination.

[0033] <Flowing the fluid material> In flowing the fluid material, an inert gas is introduced into a reactor containing the fluid material containing a calcium compound, and the fluid material is made to flow.

[0034] The reactor is a reactor capable of accommodating a fluidized material and having a certain internal space to ensure a flow path for raw materials including plastics and inert gases, and is preferably a fluidized bed.

[0035] There are no particular restrictions on the shape, structure, and size of the reactor, and they can be appropriately selected according to the purpose. However, from the viewpoint of allowing the raw materials containing plastic and the generated chemicals to flow smoothly and ensuring sufficient contact time between the raw materials containing plastic and the fluidized bed, it is preferable that the length in the flow direction of the raw materials containing plastic be longer than the length in the direction perpendicular to the flow direction, i.e., longer than the inner diameter of the reactor.

[0036] A fluidized bed is placed inside the reactor. A fluidized bed is a reactor vessel that suspends a fluidized material by passing an inert gas through it at a sufficient speed, causing the fluidized material to behave like a fluid.

[0037] <<Flowing Material>> The flowing material contains a calcium compound. The flowing material may further contain other components besides the calcium compound.

[0038] - Calcium compound - The calcium compound is not particularly limited and can be appropriately selected according to the purpose. For example, calcium, calcium salts, calcium oxides, calcium hydroxides, etc. can be mentioned. These can be used alone or in combination of two or more. Among these, as the calcium compound, calcium oxide is preferable.

[0039] As the calcium oxide, for example, calcium carbonate, calcium hydrogen carbonate, calcium hydroxide, calcium oxide, calcium nitrate, calcium sulfate, calcium phosphate, calcium oxalate, etc. can be mentioned. These can be used alone or in combination of two or more. Among these, as the calcium compound, those containing calcium oxide are preferable.

[0040] The content of calcium oxide in the calcium compound is not particularly limited and can be appropriately selected according to the purpose. Among these, the calcium compound preferably consists only of calcium oxide (that is, the content of calcium oxide in the calcium compound is 100% by mass).

[0041] From the viewpoint of using as a fluidizing agent, the shape of the calcium compound is preferably granular. The shape of the granular calcium compound may be regular or irregular.

[0042] The particle size of the calcium compound is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.3 mm or less. The particle size of the fluidizing agent is measured by the dry sieving test of ISO 2591-1:1988.

[0043] - Other components - Other components in the fluidizing agent other than the calcium compound are not particularly limited and can be appropriately selected according to the purpose. However, it is preferably a material that is stable in the temperature range of thermal decomposition during heating, does not react with carbon, hydrogen, etc. generated by the thermal decomposition of plastics, and does not react with inert gases.

[0044] There are no particular restrictions on the content of other components in the fluid material; they can be appropriately selected depending on the purpose.

[0045] <<Inert Gas>> There are no particular restrictions on the inert gas, but a gas that is stable in the heating temperature range is preferred.

[0046] Specific examples of inert gases include nitrogen gas, water vapor, carbon dioxide, and noble gases. These may be used individually or in combination of two or more. Among these, at least one of nitrogen gas and water vapor is preferred as the inert gas due to its industrial availability and low cost, with nitrogen gas being more preferred.

[0047] The flow rate of the inert gas introduced into the reactor is not particularly limited as long as it can keep the fluid material flowing, and can be appropriately selected according to the purpose. However, the cross-sectional area of ​​the inside of the reactor at the lower end of the part containing the fluid material is 1 cm². ２ The flow rate per unit area may be 5 N mL / sec or more, 6 N mL / sec or more, 7 N mL / sec or more, 8 N mL / sec or more, and may be 500 N mL / sec or less, 400 N mL / sec or less, 300 N mL / sec or less, or 200 N mL / sec or less. Here, "N" in the unit of volumetric flow rate represents the value converted to 0°C and 1 atmosphere. The flow rate of the inert gas is the flow rate of the inert gas is the aforementioned cross-sectional area 1 cm² ２ A flow rate of 5 N mL / second or more and 500 N mL / second or less per unit area ensures sufficient contact time between the raw materials containing plastic and the fluidizing agent, suppresses side reactions, and efficiently heats the reaction furnace, thereby enabling the efficient acquisition of useful components in high yield. The linear velocity of the inert gas can be determined by the method described in the examples.

[0048] <Heating> Heating involves heating the reactor. Heating may be done separately from or simultaneously with the fluidizing of the fluidizing material.

[0049] There are no particular restrictions on the method of heating the reactor, and it can be appropriately selected according to the purpose. It may be an external heating method in which the reactor is heated by heat transfer from the outside, or an internal heating method in which the fluid material is heated by resistance heating using electric heating wires or the like inside the reactor.

[0050] There are no particular restrictions on the heating temperature of the reactor, and it can be appropriately selected depending on the purpose, but it is preferably 1,000°C or lower, more preferably 990°C or lower, and even more preferably 980°C or lower. When the heating temperature of the reactor is 1,000°C or lower, useful components can be obtained efficiently in high yield. Furthermore, when the heating temperature of the reactor is 980°C or lower, the generation of methane, a by-product produced by the decomposition of plastics and difficult to utilize as a basic chemical, can be suppressed.

[0051] There are no particular restrictions on the lower limit of the heating temperature for the reactor, as long as the plastic can be decomposed, and it can be appropriately selected depending on the purpose. However, a temperature of 500°C or higher is preferred, 580°C or higher is more preferred, and 650°C or higher is even more preferred. When the lower limit of the heating temperature for the reactor is 500°C or higher, useful components can be obtained efficiently in high yield.

[0052] The upper and lower limits of the heating temperature for heating the reactor can be combined as appropriate, but 500°C to 1,000°C is preferred, 580°C to 980°C is more preferred, and 650°C to 980°C is even more preferred.

[0053] <Supplying> Supplying means supplying raw materials containing plastic to the heated reactor. This allows the raw materials containing plastic to be thermally decomposed, producing chemicals containing ethylene and propylene. From the viewpoint of thermally decomposing the raw materials containing plastic in a fluidized bed, it is preferable to supply them simultaneously with fluidizing the fluidizing agent and heating.

[0054] There are no particular restrictions on the method of supplying the raw materials containing plastic to the reactor; they may be supplied intermittently or continuously. Among these methods, continuous supply is preferred because it minimizes temperature fluctuations in the reactor.

[0055] When raw materials containing plastic are supplied to the reactor intermittently, there are no particular restrictions on the supply time, non-supply time, or intervals between these.

[0056] When supplying raw materials containing plastic to the reactor intermittently, there are no particular restrictions on the amount of plastic-containing raw materials supplied at one time. However, when supplying plastic-containing raw materials to the reactor intermittently, it is preferable to wait until the reactor temperature, which has dropped due to the previous supply, has recovered to the desired temperature before adding the plastic-containing raw materials for the second and subsequent additions, from the viewpoint of preventing the reactor temperature from dropping too low.

[0057] When raw materials containing plastic are continuously supplied to the reactor, there are no particular restrictions on the amount of raw materials containing plastic that can be supplied.

[0058] -Raw materials containing plastic- There are no particular restrictions on raw materials containing plastic, and they can be appropriately selected according to the purpose. Examples include mixed plastics containing polyolefins, aromatic plastics, and chlorine-containing plastics. These may be used individually or in combination of two or more. Furthermore, raw materials containing plastic may also contain other components as needed.

[0059] --Mixed Plastics-- There are no particular restrictions on the polyolefins included in the mixed plastics, and they can be appropriately selected depending on the purpose, but it is preferable that they include polyethylene (PE) and polypropylene (PP), which are commonly used in beverage and food containers, packaging materials, molded products, films, etc.

[0060] There are no particular restrictions on the polyolefin content in the raw materials containing plastics, and it can be appropriately selected depending on the purpose. However, it is preferably 50% to 90% by mass, more preferably 55% to 87% by mass, and even more preferably 60% to 85% by mass, relative to the total mass of the raw materials containing plastics. When the polyolefin content in the raw materials containing plastics is 50% to 90% by mass, chemical products containing ethylene and propylene can be obtained efficiently in high yield.

[0061] --Aromatic Plastics-- Aromatic plastics are plastics having an aromatic skeleton. There are no particular restrictions on aromatic plastics, and they can be appropriately selected from those commonly used for beverage and food containers, packaging materials, molded products, films, etc., depending on the purpose. Examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), acrylonitrile-butadiene-styrene copolymer, polycarbonate (PC), and polystyrene (PS). These may be contained individually or in combination of two or more. Among these, aromatic plastics preferably contain polyethylene terephthalate (PET) and polystyrene (PS). In the chemical manufacturing method of this disclosure, even if the raw material plastic contains aromatic plastics such as polyethylene terephthalate (PET) and polystyrene (PS), chemicals containing ethylene and propylene can be obtained efficiently in high yield.

[0062] --Chlorine-containing plastics-- There are no particular restrictions on chlorine-containing plastics, and they can be appropriately selected depending on the purpose, but it is preferable that they contain at least one selected from the group consisting of polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and chlorinated polyethylene (CPE), which are commonly used in beverage and food containers, packaging materials, molded products, films, etc.

[0063] There are no particular restrictions on the content of at least one selected from the group consisting of aromatic plastics and chlorine-containing plastics in the plastic, and it can be appropriately selected depending on the purpose. However, it is preferably 10% by mass or more and 50% by mass or less, more preferably 13% by mass or more and 45% by mass or less, and even more preferably 15% by mass or more and 40% by mass or less, relative to the total mass of the plastic. When the content of at least one selected from the group consisting of aromatic plastics and chlorine-containing plastics in the plastic is 10% by mass or more and 50% by mass or less, chemical products containing ethylene and propylene can be obtained efficiently in high yield. Furthermore, the lower the content of at least one selected from the group consisting of aromatic plastics and chlorine-containing plastics, the better. The lower limit may be, for example, 0.1% by mass or more, 0.5% by mass or more, 5% by mass or more, or 10% by mass or more, relative to the total mass of the plastic.

[0064] --Other Components-- There are no particular restrictions on other components contained in raw materials containing plastics, and they can be appropriately selected depending on the purpose. Examples include other plastics other than polyolefins, aromatic plastics, and chlorine-containing plastics; and materials that are normally found in waste plastics such as paper and metal. These may be contained individually or in combination of two or more types.

[0065] Other plastics are not particularly limited and can be selected as appropriate depending on the purpose, and examples include polyamide, polyurethane, and polymethyl methacrylate.

[0066] There are no particular restrictions on the content of other components in the raw material containing plastic, and they can be appropriately selected depending on the type of raw material containing plastic used. However, from the viewpoint of the yield of chemicals containing ethylene and propylene, it is preferable that the content be less than 30% by mass, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the raw material containing plastic.

[0067] From the viewpoint of reducing environmental impact, it is preferable that the raw materials containing plastic include waste plastic. When the raw materials containing plastic are waste plastic, there are no particular restrictions on the composition and composition ratio, and they can be appropriately selected according to the purpose, but it is preferable that PE is 20% to 40% by mass, PP is 20% to 40% by mass, PS is 10% to 30% by mass, and PET is 10% to 30% by mass.

[0068] As waste plastics, for example, Refuse-derived paper and plastics-densified fuel (RPF) can be used.

[0069] The structure and content of each component in raw materials containing plastics can be determined by analysis using methods such as Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), ion chromatography (IC), nuclear magnetic resonance (NMR), liquid chromatography-mass spectrometry (LC-MS), pyrolysis gas chromatography-mass spectrometry (PyGC-MS), and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOFMS).

[0070] In terms of supply, there are no particular restrictions on the state of the plastic in the raw materials supplied to the reactor, including crystalline, glassy, ​​rubbery, and liquid forms. The plastic may also be in a decomposed state. Among these, rubbery or liquid plastic is preferred because it is easier to control the supply amount.

[0071] When the plastic is crystalline or glassy, ​​there are no particular restrictions on its form, and examples include crushed plastic, pellets of crushed plastic, and chips of crushed plastic.

[0072] There are no particular restrictions on the type of plastic used for the pulverized material; it can be appropriately selected depending on the purpose, for example, in powder or flake form.

[0073] Rubber-like or liquid plastic refers to plastic that is fluid at a temperature above its melting point but below its thermal decomposition temperature. Rubber-like or liquid plastic is also called "molten plastic."

[0074] Plastic decomposition products are materials that have been broken down from plastics into smaller molecules, but their molecular weight is still larger than that of the final chemical product.

[0075] The molecular weight of rubbery or liquid plastics does not change from the molecular weight of crystalline or glassy plastics of the same composition. Therefore, plastics and their decomposition products can be distinguished by their molecular weight. As the molecular weight decreases due to decomposition, the melting point decreases, so in practice, it can be determined by the melting temperature. The melting temperature is measured by the method specified in JIS K7121-2012.

[0076] There are no particular restrictions on the melting temperature of the plastic, and it can be appropriately selected depending on the raw materials used, but 80°C to 200°C is preferred, 85°C to 195°C is more preferred, and 90°C to 190°C is even more preferred.

[0077] These raw materials, including various forms of plastic, may be used after being processed separately from the chemical manufacturing methods of this disclosure, or after being subjected to other processing as described below.

[0078] <Other Processing> The method for producing the chemicals of this disclosure may further include, as necessary, other processing other than flowing and supplying the fluidizing agent.

[0079] Other processing methods are not particularly limited and can be selected as appropriate depending on the purpose. Examples include pre-treating raw materials containing plastics, recovering chemicals obtained through supply, post-treating chemicals, separating chemicals, and reusing fluid materials.

[0080] <<Pre-treatment>> Pre-treatment involves pre-treating the raw materials containing plastic before they are supplied. By pre-treating the raw materials containing plastic to make them easier to decompose, the plastic can be decomposed more efficiently.

[0081] Examples of pretreatment include crushing the raw material containing plastic, pelletizing (chipping) the crushed raw material containing plastic, and melting the raw material containing plastic.

[0082] It is preferable to melt down raw materials containing plastics at a temperature of less than 300°C.

[0083] There are no particular restrictions on the pulverized raw materials containing plastic, and they can be appropriately selected depending on the purpose. Examples include powder and flake forms.

[0084] There are no particular restrictions on the method for obtaining pulverized material containing plastic, and any conventionally known method can be appropriately selected. For example, a method can be used in which the plastic-containing material is pulverized using a pulverizer to obtain powder or flakes.

[0085] Furthermore, there are no particular restrictions on the method of pelletizing (chipping) the pulverized material, and any conventionally known method can be appropriately selected. For example, one method is to melt-extrude the pulverized material and then cut the strand-shaped melt-extruded material to obtain chipped raw material.

[0086] The raw materials containing plastic can also be supplied in a molten state. There are no particular restrictions on the method of melting the raw materials containing plastic, and any conventionally known method can be appropriately selected. For example, a method of continuously supplying the materials to the decomposition process using a molten extruder can be used.

[0087] <<Recovery>> Recovery involves recovering the liquid substances and gases that are products containing the chemicals obtained through supply. There are no particular restrictions on the recovery method, and a method can be appropriately selected from known methods depending on the type of product obtained. For example, gaseous products can be separated by atmospheric pressure or pressurized distillation, and liquid hydrocarbons can be separated by atmospheric pressure or reduced pressure distillation.

[0088] <<Post-treatment of chemicals>> Post-treatment of chemicals is a process of decomposing by-products in chemicals generated by the thermal decomposition of raw materials, including plastics. It is preferable to perform post-treatment of chemicals after the recovery of the chemicals.

[0089] Post-treatment methods for chemicals include, for example, the removal of halogen compounds. Methods for removing halogen compounds include a fixed bed filled with an oxide or hydroxide of one metal selected from alkali metals and alkaline earth metals, or a method of passing an aqueous solution of the oxide or hydroxide of the said metal through the bed.

[0090] <<Separation>> Separation involves separating only the useful components from the recovered liquid substance and gas, and removing unwanted components.

[0091] The substances produced by the chemical manufacturing method of this disclosure are chemicals containing ethylene and propylene, preferably chemicals containing olefins having 2 to 4 carbon atoms and aromatic hydrocarbons, but paraffins having 2 to 4 carbon atoms may be produced as a by-component.

[0092] In terms of separation, there are no particular restrictions on the method used to separate the useful components from the minor components, and a method can be appropriately selected from known methods depending on the type of product obtained or the type of minor components.

[0093] The above chemical manufacturing method allows for the efficient production of chemicals containing ethylene and propylene in high yield. The produced chemicals can be used as basic chemicals suitable for chemical recycling.

[0094] (Chemical Manufacturing Apparatus) The chemical manufacturing apparatus of the present disclosure comprises a reactor containing a fluid material containing a calcium compound; a raw material supply unit connected to the reactor and supplying raw materials containing plastic to the reactor; an inert gas supply unit connected to one end of the reactor and arranged to supply an inert gas to the fluid material from a direction opposite to the direction of gravity; and a heating unit for heating the reactor. The chemical manufacturing apparatus of the present disclosure may further include other components as necessary.

[0095] The chemical manufacturing apparatus of the present disclosure can suitably carry out the chemical manufacturing method of the present disclosure.

[0096] Embodiments of the chemical manufacturing apparatus of this disclosure will be described below with reference to the drawings. Figure 1 is a schematic cross-sectional view showing an example of the chemical manufacturing apparatus of this disclosure. The embodiments shown below are illustrative of apparatus for realizing the technical concept of this disclosure and do not limit this disclosure to the following. Furthermore, the dimensions, materials, shapes, numbers, relative arrangements, etc. of the components described below are merely illustrative examples and are not intended to limit the scope of this disclosure unless otherwise specified. Note that the size and positional relationships of the members shown in each drawing may be exaggerated to clarify the explanation. In addition, in the following explanation, the same name and reference numeral indicate the same or similar member, and detailed explanations are omitted as appropriate. In order to avoid making the drawings excessively complex, schematic diagrams that omit the illustration of some elements may be used, or end view diagrams showing only the cut surface may be used as cross-sectional views.

[0097] Furthermore, the following description uses terms that indicate specific directions or positions as needed (e.g., "up," "down," "side," "top surface," "bottom surface," "side," "X," "Y," "Z," and other terms including these terms). However, the use of these terms is solely to facilitate understanding of the invention with reference to the drawings, and the meaning of these terms does not excessively limit the technical scope of the present invention. For example, if "top surface" is mentioned, the invention must not always be used in a way that faces upwards.

[0098] In FIG. 1, the vertical direction is defined as the Y-axis direction, the direction substantially orthogonal to the Y-axis direction is defined as the X-axis direction, and the direction substantially orthogonal to the X-axis direction and the Y-axis direction is defined as the Z-axis direction. The X-axis, the Y-axis, and the Z-axis are mutually orthogonal. However, this direction is merely an example, and the direction of the chemical manufacturing apparatus of the present disclosure is not limited thereto.

[0099] The chemical manufacturing apparatus 100 (hereinafter sometimes abbreviated as "manufacturing apparatus 100") includes a reactor 1 that houses a fluid material 2 containing a calcium compound, a raw material supply unit 3 that supplies a raw material M containing plastic to the reactor 1, an inert gas supply unit 4 that supplies an inert gas G to the reactor 1, and a heating unit 5 that heats the reactor 1.

[0100] <Reactor 1> The reactor 1 is a member that houses the fluid material 2. In the reactor 1, the fluid material 2 disposed inside the reactor 1 is heated by the heating unit 5 to heat the raw material M (hereinafter sometimes abbreviated as "raw material M") containing plastic supplied to the inside of the reactor 1.

[0101] The material of the reactor 1 is not particularly limited as long as it is stable in the inner side of the reactor 1, that is, the surface temperature and atmosphere on the side where the raw material M of the reactor 1 is housed. For example, inorganic compounds such as alumina (Al ２ O ３ ), zirconia (ZrO ３ ), silicon carbide (SiC), silicon nitride (Si ３ N ４ ), mullite (3Al ２ O ３ ·2SiO ２ ) can be used, and alloys such as SUS310S, Inconel (registered trademark), and Hastelloy (registered trademark) can also be used.

[0102] The structure, shape, material, and size of the reactor 1 are not particularly limited as long as it can house the fluid material 2 and allow the raw material M to flow through, and can be appropriately selected according to the purpose.

[0103] Examples of the shape of the reactor 1 include cylindrical, rectangular parallelepiped, conical, frustoconical, and columnar shapes in which the cross-sectional shape perpendicular to the longitudinal direction of the reactor 1 is polygonal.

[0104] Furthermore, regarding the size of the reactor 1, it is preferable that the direction of flow of the raw material M is perpendicular to the direction of flow, i.e., longer than the inner diameter of the reactor 1, from the viewpoint of allowing the raw material M and the generated chemical product R to flow smoothly and ensuring sufficient contact time between the raw material M and the fluidized bed of the fluidizing agent 2.

[0105] In order to retain the fluid material 2 inside the reactor 1, it is preferable to place a stopper 10 inside the reactor 1 (for example, inside a pipe) using a mesh tray or quartz wool that allows an inert gas G such as quartz wool and the chemical product R to flow through.

[0106] The structure, shape, material, and size of the stopper 10 are not particularly limited, as long as they do not allow the fluid material 2 to pass through, but do allow the inert gas G, raw material M, or chemical product R to pass through. They can be appropriately selected according to the purpose, and examples include quartz wool, a sieve, a mesh, and a dispersion plate. These may be used individually or in combination of two or more types.

[0107] The fluid material 2 is as described in the section (Method of Manufacturing Chemicals) of this disclosure.

[0108] <Raw Material Supply Unit 3> The raw material supply unit 3 is connected to the reactor 1 and is a component that supplies raw materials M, including plastic, to the reactor 1. The raw material supply unit 3 includes a raw material distribution unit 3a for circulating the raw materials M, a raw material input unit 3b for introducing the raw materials M into the reactor 1, and so on. The raw material supply unit 3 may supply the raw materials M to the reactor 1 using a known pump or the like.

[0109] The raw material distribution section 3a is connected to the reactor 1. In this disclosure, "connection" of the raw material distribution section 3a to the reactor 1 means that the inside of the raw material distribution section 3a and the inside of the reactor 1 are in communication so that the raw material M can pass through them.

[0110] Furthermore, the raw material supply unit 3 may have a raw material supply stopper, such as a stopper, that can stop the supply of raw materials M, including plastic. If a raw material supply stopper is provided, plastic can be supplied to the reactor 1 intermittently. The raw material supply stopper can be located, for example, at the inlet of the raw material input unit 3b.

[0111] There are no particular restrictions on the material of the raw material supply unit 3; for example, it can be appropriately selected from the same materials as those used for the reactor 1, depending on the purpose.

[0112] The shape, structure, and size of the raw material supply unit 3 are not particularly limited as long as it can be connected to the reactor 1 and supply raw materials M to the reactor 1. They can be appropriately selected according to the purpose, for example, a cylindrical shape or a rectangular parallelepiped. Also, if a part of the reactor 1 has an opening, this opening can be used as the raw material supply unit 3.

[0113] The location of the raw material supply unit 3 is not particularly limited as long as it can be connected to the reactor 1 and supply raw materials M to the fluid material 2. It can be appropriately selected depending on the type of raw material M, but it is preferable that it be in a position where the raw materials M can be supplied from above the fluid material 2. In Figure 1, the raw material supply unit 3 is shown to be located on the upper surface in the longitudinal direction of the reactor 1, but it may also be located on the side of the reactor 1.

[0114] <Inert Gas Supply Unit 4> The inert gas supply unit 4 is a component connected to one end of the reactor 1 and arranged to supply inert gas G to the fluid material 2 from a direction opposite to the direction of gravity. Examples of the inert gas supply unit 4 include an inert gas flow section 4a through which the inert gas G flows, and a pump 4b that flows the inert gas G in a fixed amount for a fixed period of time.

[0115] The inert gas flow section 4a is connected to the reactor 1. In this disclosure, "connection" of the inert gas flow section 4a to the reactor 1 means that the inside of the inert gas flow section 4a and the inside of the reactor 1 are in communication and allow the inert gas G to pass through.

[0116] The position of the inert gas supply unit 4 is not particularly limited as long as it can be connected to the reactor 1 and can allow the fluidizing material 2 to flow. The position can be appropriately selected depending on the type of inert gas G. However, from the viewpoint of allowing the fluidizing material 2 to flow, it is preferable to position it in a location where the inert gas G can be supplied to the fluidizing material 2 from a direction opposite to the vertical. For example, as shown in Figure 1, the inert gas supply unit 4 can be placed on the lower surface of the reactor 1 in the Y-axis direction. However, the position of the inert gas supply unit 4 is not limited to this. As long as it can be connected to the reactor 1 and can allow the fluidizing material 2 to flow, the inert gas supply unit 4 may also be placed on the upper surface of the reactor 1 in the Y-axis direction, or on the side surface of the reactor 1 in the X-axis direction.

[0117] As for the type of inert gas G, those described in the section (Method of Manufacturing Chemical Products) of this disclosure can be used.

[0118] <Heating section 5> The heating section 5 is a component that heats the reactor 1. There are no particular restrictions on the structure, shape, material, and size of the heating section 5 as long as it can heat the reactor 1, and it can be appropriately selected according to the purpose.

[0119] There are no particular restrictions on the heating method of the heating section 5. It may be an external heating method in which the reactor 1 is heated by heat transfer from the outside, or an internal heating method in which the reactor 1 is heated from inside. For the heating section 5 of the external heating method, for example, a known electric furnace can be used. For the heating section 5 of the internal heating method, for example, a resistance heating method can be used in which a resistor such as an electric heating wire is placed inside the reactor 1 and heat is generated by applying a voltage to the resistor.

[0120] The temperature of the fluid material 2 can be measured by inserting a thermocouple into the center of the fluid material 2.

[0121] <Other Components> There are no particular restrictions on other components, and they can be appropriately selected according to the purpose. Examples include a product extraction unit 6, a storage unit 7, a cooling unit 8, a gaseous product recovery unit 9, and a measuring unit for measuring the yield of useful components.

[0122] <<Product Extraction Section 6>> The product extraction section 6 is a component that extracts the chemical product R from the reactor 1. Examples of the product extraction section 6 include a product distribution section 6a through which the chemical product R flows, and a pump 6b that flows the chemical product R in a fixed amount for a fixed period of time.

[0123] The product extraction unit 6 is connected to the reactor 1. In this disclosure, "connection" of the product extraction unit 6 to the reactor 1 means that the inside of the product flow section 6a of the product extraction unit 6 and the inside of the reactor 1 are in communication so that the chemical product R can pass through them.

[0124] The structure, shape, material, and size of the product extraction section 6 are not particularly limited as long as they can extract the chemical product R processed in the reactor 1, and can be appropriately selected according to the purpose. Examples include cylindrical shapes and rectangular parallelepipeds. Furthermore, if a part of the reactor 1 has an opening, this opening can also be used as the product extraction section 6.

[0125] The location of the product extraction unit 6 is not particularly limited as long as it can be connected to the reactor 1, and can be appropriately selected depending on the type of chemical R. Figure 1 shows the product extraction unit 6 positioned on the lower surface in the Y-axis direction of the reactor 1, but the product extraction unit 6 may also be positioned on the upper surface in the Y-axis direction of the reactor 1, or on the side surface in the X-axis direction of the reactor 1.

[0126] In reactor 1, chemical product R is produced from raw material M, so raw material M and chemical product R may be mixed inside reactor 1. Therefore, product extraction unit 6 may extract not only chemical product R, but also a mixture of raw material M and chemical product R. In addition, if by-products are produced in reactor 1, product extraction unit 6 may also extract the by-products.

[0127] <<Storage Section 7>> The storage section 7 is a component for storing raw materials M, including plastic.

[0128] The structure, shape, material, and size of the storage section 7 are not particularly limited as long as they can store the raw material M, and can be appropriately selected according to the purpose.

[0129] There are no particular restrictions on the number of storage units 7; there may be one or multiple units. If the manufacturing apparatus 100 has multiple storage units 7, for example, multiple types of raw materials M can be stored separately. For example, if the raw material M is a plastic containing polyolefin and at least one selected from the group consisting of aromatic plastics and chlorine-containing plastics, it can be used to store plastics with different compositions and content rates of each component.

[0130] <<Cooling Section 8>> The cooling section 8 is a component that cools the chemical product R obtained by passing through the reactor 1. By cooling the chemical product R, the liquid component of the chemical product R can be recovered as a product within the cooling section.

[0131] Examples of the cooling section 8 include a cooling trap 8a for cooling the chemical product R, and a cooling section 8b for cooling the cooling trap 8a. The structure, shape, material, and size of the cooling trap 8a and the cooling section 8b are not particularly limited as long as they can cool the chemical product R, and can be appropriately selected according to the purpose.

[0132] The cooling trap 8a may contain an organic solvent 8c for dissolving the chemical product R. The organic solvent 8c can condense the useful components in the chemical product R, especially the liquid useful components. A non-aqueous solvent is preferred as the organic solvent for dissolving the chemical product R. Examples of non-aqueous solvents include aromatic organic solvents such as monochlorobenzene, o-dichlorobenzene, and mesitylene. It is preferable that the outlet of the product extraction section 6 is placed in the organic solvent 8c so that the chemical product R (e.g., the generated gas) bubbles in the organic solvent 8c.

[0133] The useful components dissolved in a non-aqueous solvent can be suitably separated by further distillation at atmospheric pressure.

[0134] The cooling section 8b is not particularly limited as long as it can cool the cooling trap 8a, and may, for example, contain a refrigerant 8d. Examples of refrigerant 8d include ice water.

[0135] <<Gaseous Product Recovery Unit 9>> The gaseous product recovery unit 9 is a component that recovers gaseous products from the chemical product R containing useful components manufactured by the manufacturing apparatus 100. The gaseous product recovery unit 9 may consist of only one unit or two or more units.

[0136] There are no particular restrictions on the structure, shape, material, and size of the gaseous product recovery unit 9, and they can be appropriately selected according to the purpose and the type of chemical product R, including known containers.

[0137] Furthermore, the gaseous product recovery unit 9 may contain a solvent capable of separating useful components. There are no particular restrictions on the solvent, and it can be appropriately selected depending on the type of useful component to be recovered. For example, ethanol, hexane, dimethylformamide, cyclopentane, and water can be used as solvents for extracting useful components from the liquid chemical product R.

[0138] The useful components in the gaseous product can be suitably separated by further pressurized distillation.

[0139] <<Measurement Unit>> The measurement unit is a component that measures the yield of useful components in a chemical product R containing useful components manufactured by the manufacturing apparatus 100.

[0140] The measuring unit may be located inside the manufacturing apparatus 100, or it may be connected to and provided outside the manufacturing apparatus 100.

[0141] The measuring unit is not particularly limited as long as it can measure the yield of useful components in the chemical product R, and any known measuring device may be used. Examples of known measuring devices include flame ionization detectors (FIDs) and thermal conduction detectors (TCDs).

[0142] There are no particular restrictions on the structure, shape, material, and size of the measuring section; they can be appropriately selected according to the purpose and type of product.

[0143] [Example of operation of the manufacturing apparatus] Next, an example of the operation of the manufacturing apparatus 100 will be described. The manufacturing apparatus 100, for example, performs the function of fluidizing the fluid material 2 in the reactor 1 by supplying an inert gas G from the direction opposite to the direction of gravity using an inert gas supply unit 4. Then, the heating unit 5 heats the reactor 1 to a desired temperature, thereby performing the heating function in the method of manufacturing the compound of the disclosure. While the reactor 1 is being heated by the heating unit 5, the raw material M containing plastic stored in the storage unit 7 is supplied to the reactor 1 by the raw material supply unit 3, thereby performing the supply function in the method of manufacturing the compound of the disclosure. The reactor 1 is a fluidized bed reactor in the method of manufacturing the compound of the disclosure.

[0144] The chemical product R, which is a product containing useful components obtained by heating, can be recovered and separated in the cooling unit 8 and the gaseous product recovery unit 9 in the method for producing the compound of this disclosure.

[0145] The chemicals produced by the manufacturing apparatus 100 of this disclosure are as described in the method for producing compounds of this disclosure.

[0146] Furthermore, various processes in the manufacturing apparatus 100, such as the timing and speed of supplying raw material M by the raw material supply unit 3, the timing and speed of supplying inert gas G by the inert gas supply unit 4, and the timing, heating temperature, and heating time of heating by the heating unit 5, are performed by processing signals to each unit by the signal processing unit. The signal processing unit is an electronic circuit such as a CPU, FPGA, or ASIC, and performs the various processes described in this specification by executing instruction codes stored in memory or by designing the circuit for special applications.

[0147] (Fluidizing agent and method of use thereof) The fluidizing agent of this disclosure is a fluidizing agent used in a fluidized bed for the thermal decomposition of raw materials including plastics, and contains a calcium compound.

[0148] The raw materials, including calcium compounds, fluids, and plastics, are as described in the section (Method of Manufacturing Chemicals) of this disclosure.

[0149] Furthermore, the method of using the aforementioned fluidizing agent is also included in this disclosure. Specifically, this disclosure relates to a method of using a fluidizing agent containing a calcium compound in a fluidized bed for the thermal decomposition of raw materials including plastics. This disclosure also relates to a method of using a fluidizing agent used to produce chemicals by thermal decomposing raw materials including plastics, wherein the fluidizing agent contains a fluidized calcium compound.

[0150] The present disclosure will be specifically described below with reference to test examples, embodiments, and comparative examples, but the present disclosure is not limited in any way to these test examples, embodiments, and comparative examples.

[0151] (Test Example 1) <Preparation of the apparatus> The manufacturing apparatus 100 shown in Figure 1 was prepared. Specifically, a sieve was placed in the center of a quartz tube with an inner diameter of 15 mm and a height of 550 mm, which served as the reaction furnace 1. Quartz wool was laid down, a stopper 10 was placed, and then the fluidizing agent 2 was added. The type and amount of fluidizing agent 2 used were those described in Example 1, Example 2, or Comparative Example 1 in Table 1. The quartz tube was placed inside a cylindrical electric furnace (product name: ARF-30MC, manufactured by Asahi Rika Seisakusho Co., Ltd.) which was installed vertically, and the quartz tube was positioned so that the fluidizing agent 2 was in the center of the cylindrical electric furnace. The electric furnace is an external heating type heating unit 5. A manual powder feeding device (airless feed cock, manufactured by Asahi Seisakusho Co., Ltd.) as the raw material input section 3b of the raw material supply section 3 and one end of the gas extraction piping as the product extraction section 6 for extracting gas as the chemical product R were connected to the top of the electric furnace. In addition, a gas inlet as the inert gas supply section 4 was connected to the bottom of the electric furnace. The other end of the gas extraction pipe was connected to the inlet side of a cooling trap 8a containing 15 mL of o-dichlorobenzene (reagent grade, manufactured by Kanto Chemical Co., Ltd.) as the organic solvent 8c. The cooling trap 8a was placed in a cooling section 8b containing ice water as the refrigerant 8d. One end of another gas extraction pipe was connected to the outlet side of the cooling trap 8a, and the other end of the other gas extraction pipe was connected to a gas bag (volume 10 L) as the gas product recovery section 9. A thermocouple was inserted into the center of the fluid material 2 filled in a quartz tube. Nitrogen gas as the inert gas G was blown in from the gas inlet at a flow rate of 1,600 mL / min, and the electric furnace temperature was set to 800°C to start heating.

[0152] To confirm the behavior of the fluid material 2, a blank test was conducted by introducing only nitrogen gas as the inert gas G, without adding the raw material M. As a result, it was confirmed that the fluid material 2 rose to a height of 7 cm from the sieve in the center of the quartz tube.

[0153] (Example 1) <Preparation of mixed plastic> Polyethylene (HDPE, Hyzex® 1300J, manufactured by Prime Polymer Co., Ltd.), polypropylene (Prime Polypro® J108M, manufactured by Prime Polymer Co., Ltd.), polystyrene (PSJ-Polystyrene® SGP10, manufactured by PS Japan Co., Ltd.), and polyethylene terephthalate (PET, NEH-2070, manufactured by Unitika Ltd.) were mixed in a ratio of PE:PP:PS:PET = 32:32:20:16 (w / w) to prepare a mixed plastic.

[0154] <Decomposition of Mixed Plastics> The mixed plastics were decomposed using the apparatus described in Test Example 1. 5 g of calcium oxide (product name: CALFUSE®, particle size: 1 mm to 0.3 mm, manufactured by Tateho Chemical Industry Co., Ltd.) (shown as "Calcium Oxide A" in Table 1) was used as the fluidizing agent 2. After the furnace reached the set temperature of 800°C and the temperature stabilized, 0.8 g of mixed plastics was supplied into the quartz tube from a manual powder feeder over 5 minutes while nitrogen gas was introduced from the gas inlet at a flow rate of 1,600 mL / min. The liquid components were then collected in the cooling trap 8a, and the gaseous components were collected in the gas bag. Five minutes after the supply of mixed plastics was completed, the gas bag was detached from the apparatus. The cooling trap 8a was returned to room temperature (25°C ± 5°C) and left for approximately 3 minutes before being detached from the apparatus.

[0155] (Example 2) The mixed plastic was decomposed in the same manner as in Example 1, except that the fluidizing agent was changed to calcium oxide (product name: CALFUSE®, particle size: 0.3 mm or less, manufactured by Tateho Chemical Industry Co., Ltd.) (shown as "Calcium Oxide B" in Table 1).

[0156] (Comparative Example 1) The mixed plastic was decomposed in the same manner as in Example 1, except that the fluidizing agent was changed to a conventional fluidizing agent, silica sand (product name: Ube Silica Sand No. 6, particle size: 0.6 mm to 0.07 mm, manufactured by Ube Sand Industries Co., Ltd.).

[0157] <<Analysis of Gas Bag Contents>> In Example 1, Example 2, and Comparative Example 1, the yield of useful components in the pyrolysis gas recovered in the gas bag was determined as a ratio (mass%) to the amount of raw material containing plastic used, by the following method.

[0158] In the gas bag, cyclopentane (>98.0%, density 0.75 g / cm³) was used as an internal standard substance. ３ 40 μL of (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The gas bag was heated to approximately 40°C to completely vaporize the contents, and then the contents were mixed by gently kneading the gas bag. The obtained contents were used as an analytical sample and analyzed by gas chromatography (GC) under the following GC analysis conditions. The ratio of the peak area of ​​cyclopentane to the peak area of ​​each component was used to determine the proportion of each component (Cmol%) relative to carbon atoms in the pyrolysis gas in the gas bag. The mass of each component in the pyrolysis gas in the gas bag was calculated from this value and the amount of cyclopentane (40 μL) added to the gas bag, and the yield (mass%) relative to the raw material M was determined. The results are shown in Table 1. [GC Analysis Conditions] ・Instrument: Nexus GC-2030 (Shimadzu Corporation) ・Column: Rt-Alumina BOND (Diameter: 0.32 mm, Length: 30 m, Restek) ・Carrier gas type: Ar ・Carrier gas flow rate: 360 mL / min ・Injection temperature: 200°C ・Sample injection volume: 1 mL ・Split ratio: 1 / 200 ・Column temperature: Held at 120°C for 9 minutes, then increased to 200°C at 10°C / min, and held at 200°C for 30 minutes.

[0159] • Detector: Flame ionization detector (FID) • Detector temperature: 200°C

[0160] <<Analysis of contents of cooling trap 8a>> In Example 1, Example 2, and Comparative Example 1, the yield of useful components in the pyrolysis components recovered in the cooling trap 8a was determined as a ratio (mass%) to the amount of raw material containing plastic using the following method.

[0161] The contents of cooling trap 8a were transferred to a sample vial. 2 mL of o-dichlorobenzene (reagent grade, manufactured by Kanto Chemical Co., Ltd.) was added to the nearly empty cooling trap 8a to dissolve the remaining contents, which were then transferred to the sample vial. This process was repeated three times to thoroughly wash the cooling trap 8a. Approximately 0.3 g of cyclopentane (>98.0%, manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed and added to the sample vial as an internal standard to prepare the analytical sample, which was then analyzed by gas chromatography (GC) under the following GC analysis conditions. The ratio of the peak area of ​​cyclopentane to the peak area of ​​each component was used to determine the carbon-carbon-based percentage (Cmol%) of each component in the pyrolysis components in cooling trap 8a. The mass of each component in the pyrolysis components in cooling trap 8a was calculated from this value and the amount of cyclopentane (0.3 g) added to the sample vial, and the yield (mass%) relative to the raw material M was determined. The results are shown in Table 1. [GC Analysis Conditions] • Instrument: Nexus GC-2030 (Shimadzu Corporation) • Column: DB-1 (Diameter: 0.25 mm, Length: 30 m, Agilent Technology) • Carrier Gas Type: He • Carrier Gas Flow Rate: 97 mL / min • Injection Temperature: 350°C • Sample Injection Volume: 1 μL • Split Ratio: 1 / 50 • Column Temperature: Temperature increase program set in the following order: 35°C (10 mins) → Increase (5°C / min) → 350°C (10 mins) • Detector: Flame Ionization Detector (FID) • Detector Temperature: 350°C

[0162] In Table 1, "Yield of useful components" refers to the ratio of the mass of each product listed in Table 1 to the mass of the mixed plastic as raw material M.

[0163] Furthermore, in Table 1, the "Increase in Total Yield of Ethylene and Propylene" indicates the ratio of the total yield of ethylene and propylene in Example 1 or Example 2 to the total yield of ethylene and propylene in Comparative Example 1. If the increase in the total yield of ethylene and propylene exceeds 100%, it is determined that the fluid material containing the calcium compound has a higher ethylene and propylene production efficiency than conventional fluid materials.

[0164] Furthermore, in Table 1, "total yield of useful components" is the ratio of the mass of the product, which consists of olefins with 2 to 4 carbon atoms and useful aromatic hydrocarbons, to the mass of the mixed plastic as raw material M. "Useful components" refers to ethylene, propylene, olefins with 4 carbon atoms (trans-2-butene, 1-butene, 2-methylpropene, cis-2-butene, 1,3-butadiene, and isobutene), and useful aromatic hydrocarbons (benzene, toluene, ethylbenzene, three positional isomers of xylene (p-xylene, m-xylene, and o-xylene), and styrene).

[0165] Furthermore, in Table 1, "(D) / (C) (NmL / cm)" ２ "Seconds" refers to the internal cross-sectional area of ​​the reactor 1 at the lower end of the part containing the fluid material 2, 1 cm². ２ This represents the flow rate of inert gas per unit. Since the unit of the inert gas flow velocity (D) is converted, the actual calculation formula is (D) / 60 / (C).

[0166]

[0167] From a comparison between Example 1, Example 2, and Comparative Example 1, it was found that using a fluidizing agent containing a calcium compound improved the yield of ethylene and propylene. In particular, in Example 2, which used calcium oxide with a particle size of 0.3 mm or less, the yield of ethylene and propylene was greatly improved.

[0168] As described above, this disclosure has been explained based on specific embodiments and examples, but these embodiments and examples are merely presented as examples, and this disclosure is not limited to the above embodiments and examples. The above embodiments can be implemented in various other forms, and various combinations, omissions, substitutions, additions, modifications, etc., are possible without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents.

[0169] This international application claims priority under Japanese Patent Application No. 2024-226827, filed on 23 December 2024, which is incorporated herein by reference to the entire contents of Japanese Patent Application No. 2024-226827.

[0170] 100: Manufacturing equipment 1: Reactor 2: Fluidized material 3: Raw material supply section 3a: Raw material distribution section 3b: Raw material input section 4: Inert gas supply section 4a: Inert gas distribution section 4b: Pump 5: Heating section 6: Product extraction section 6a: Product distribution section 6b: Pump 7: Storage section 8: Cooling section 8a: Cooling trap 8b: Cold retention section 8c: Organic solvent 8d: Refrigerant 9: Gaseous product recovery section 10: Stopper M: Raw material G: Inert gas R: Chemicals

Claims

1. A method for producing a chemical product, comprising: introducing an inert gas into a reactor containing a fluid material containing a calcium compound and causing the fluid material to flow; heating the reactor; and supplying a raw material containing plastic to the heated reactor, wherein the chemical product contains ethylene and propylene.

2. The method for producing a chemical product according to claim 1, wherein the calcium compound includes calcium oxide.

3. The method for producing a chemical product according to claim 1 or claim 2, wherein the particle size of the fluid material is 0.3 mm or less.

4. The method for producing a chemical product according to any one of claims 1 to 3, wherein the heating temperature of the reactor is 650°C or more and 1,000°C or less.

5. A method for producing a chemical product according to any one of claims 1 to 4, wherein the raw material containing the plastic includes a mixed plastic containing polyethylene and polypropylene.

6. A chemical manufacturing apparatus comprising: a reactor containing a fluid material containing a calcium compound; a raw material supply unit connected to the reactor and supplying raw materials containing plastic to the reactor; an inert gas supply unit connected to one end of the reactor and arranged to supply inert gas to the fluid material from a direction opposite to the direction of gravity; and a heating unit for heating the reactor.

7. The apparatus for producing a chemical product according to claim 6, wherein the calcium compound comprises calcium oxide.

8. A fluidizing agent used in a fluidized bed for the thermal decomposition of raw materials including plastics, characterized by containing a calcium compound.

9. The fluid material according to claim 8, wherein the calcium compound comprises calcium oxide.

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